Hydrocarbon conversion catalyst and process using said catalyst

ABSTRACT

An improved hydrocarbon conversion catalyst consisting essentially of: (A) an intermediate pore size silicaceous crystalline molecular sieve component substantially free of any catalytic loading metal; and (B) a matrix consisting essentially of (a) a gel selected from silica-alumina, silica-alumina-titania and silica-alumina-zirconia polygels, and (b) a hydrogenating component; and a process using said catalyst.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. patent application Ser. No. 160,033 (now U.S. Pat. 4,313,817), filed June 16, 1980 which is a continuation-in-part of U.S. patent application Ser. No. 21,751 filed Mar. 19, 1979, now abandoned, the disclosures of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to an improved catalyst and to hydrocarbon conversion processes using said catalyst in connection with petroleum distillates and solvent-deasphalted residua feeds to produce high-value lube oil stocks and fuel products including gasoline.

PRIOR ART

It is known that a catalyst may comprise a crystalline aluminosilica zeolite componenet associated with other catalyst components. It is also known that at least some of said other catalyst components may be in the form of a matrix in which the zeolite component is dispersed. It is also known that such catalysts may be used for such reactions as catalytic cracking, hydrocracking, and hydrodesulfurization. Representative prior art patents disclosing one or more of the foregoing matters include: U.S. Pat. Nos. 3,140,251, 3,141,253, 3,758,402, and 3,535,225. There is a continuing search for further improvements in such catalysts, and in similar multi-component catalysts, particularly for hydrocracking usage.

The present invention will best be understood, and advantages thereof will be apparent, from the following description.

SUMMARY OF THE INVENTION

In one aspect of the invention herein a composition is provided comprising a catalyst composite containing:

(A) A porous amorphous matrix selected from the group consisting of alumina-silica, alumina-silica-titania and alumina-silica-zirconia polygels, said gel having an alumina-to-silica weight ratio in the range of from about 0.2-20 to 1, respectively;

(B) a hydrogenation component of (1) nickel or cobalt or any combination thereof in an amount, calculated as metal, in the range of from about 1 to 10 weight percent of said matrix, and (2) molybdenum or tungsten, or any combination thereof, in an amount, calculated as metal in the range of from about 5 to 25 weight percent of said matrix, said component being (1) in the form of metal or oxide or sulfide or any combination thereof and (2) dispersed through said matrix; and

(C) a finely divided intermediate pore size silicaceous crystalline molecular sieve component substantially in the ammonium or hydrogen form, said zeolite being (1) substantially free of such hydrogenating component and (2) dispersed through said matrix.

In a preferred aspect of the invention, the matrix of the composition described above contains (1) at least 15 weight percent of silica and (2) an amount of titania, calculated as metal, in the range of from about 1 to 10 weight percent, the compounds containing an amount of the zeolite in the range of from about 1 to 50 weight percent and a surface area above about 200 m² /g. The preferred molecular sieve is a zeolite component of the ZSM-5 type.

Other preferred aspects of the invention include the above-described composition wherein the amount of zeolite is about 17%, the hydrogenating component is nickel and tungsten in amounts of about 7 and 17 weight percent respectively and the matrix contains about 7 weight percent of titania.

In a yet further aspect of the invention herein, the above-described catalyst is contacted with a hydrocarbon feed containing substantial amounts of materials boiling above 95° C. and selected from the group consisting of petroleum distillates, solvent-deasphalted residua, and shale oils, in a reaction zone with hydrogen and the catalyst under hydrocarbon hydrocracking conditions, and preferred variations thereof wherein the catalyst is more particularly described, for example in terms of silica, titania, and zeolite contents.

Other preferred aspects of the invention will be clear from the description to follow and of the appended claims.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE shows the effect of nitrogen upon catalyst activity.

EMBODIMENT

In a preferred embodiment a typical vacuum gas oil feed is hydrocracked under low-pressure hydrocracking conditions which are maintained at a severity sufficient to provide about a 16% conversion of the feed to product which boils below 315° C. The feed is a paraffinic hydrofined distillate which is the 371° C.+ portion of an Arabian light vacuum gas oil hydrocracked to a liquid product of which 50 volume percent boils below 371° C. The 371° C.+ portion has a nitrogen-containing impurity content of about 7 ppmw and the following inspections:

    ______________________________________                                         Gravity, °API   35.4                                                    Sulfur, ppm          33                                                        Pour Point, °C.                                                                              29                                                        Hydrocarbon Distribution, LV %                                                 Paraffins            29                                                        Naphthenes           44                                                        Aromatics            25                                                        Sulfur Compounds      2                                                        Distillation, %, °C.                                                    5/30                 391/413                                                   50/70                433/455                                                   90/EP                485/521                                                   ______________________________________                                    

The freshly prepared catalyst in which the zeolite is a ZSM-5 in the H-form and substantially free of hydrogenating components has the following composition:

    ______________________________________                                                Component                                                                              Wt. %                                                           ______________________________________                                                Ni       7                                                                     W       17                                                                     SiO.sub.2                                                                              22                                                                     Al.sub.2 O.sub.3                                                                       25                                                                     TiO.sub.2                                                                               7                                                                     H-ZSM-5 17                                                              ______________________________________                                    

In the process the initial or start-up temperature using a freshly prepared catalyst is about 284° C. and the process is carried out under the following additional conditions:

    ______________________________________                                         Pressure, Atm. g.   41                                                         LHSV, V/V/Hr        2.2                                                        Hydrogen Rate, SCM/m.sup.3                                                                         1780                                                       ______________________________________                                    

The feed conversion level to product boiling below 315° C. is about 16%. In order to maintain the conversion level, the temperature is gradually increased over a period of about 320 hours until it reaches about 310° C., after which little or no further increase is required during the more useful portion of the catalyst life-cycle (e.g., the period between start-up and regeneration or successive regenerations).

A typical product stream for a low nitrogen feedstock has the following composition:

    ______________________________________                                                Product, Wt. %                                                          ______________________________________                                                C.sub.1 -C.sub.2                                                                         trace                                                                C.sub.3 -C.sub.4                                                                         6                                                                    C.sub.5 -83° C.                                                                   3                                                                    83-315° C.                                                                        7                                                                    315° C.+                                                                          84                                                            ______________________________________                                    

The separated 315° C.+ fraction has a pour point of about 2° C.

The Catalyst

The catalyst required herein may be prepared by any suitable method whereby the molecular sieve component is present in an amorphous siliceous cracking matrix and is substantially free of catalytic hydrogenating components. In a preferred method, the molecular sieve in the H-form is added to a slurry of a silica-alumina cogel containing the desired hydrogenating components in the form of precipitated oxides and/or hydroxides (see, for example, U.S. Pat. No. 3,535,225--J. Jaffe--which is incorporated herein by reference). Preferably the matrix is selected from the group consisting essentially of alumina-silica, alumina-silica-titania and alumina-silica-zirconia polygels having an alumina-to-silica weight ratio in the range of from about 0.2-20 to 1, respectively. Gels which contain titania, zirconia, and the like moderators desirably contain them in an amount, calculated as metal, in the range of from about 1 to 10 weight percent.

By "intermediate pore size silicaceous crystalline molecular sieve," as used herein, is meant two classes of silica containing crystalline materials. The first class includes materials which, in addition to silica, contain significant amounts of alumina. These crystalline materials are usually called "zeolites," i.e., crystalline aluminosilicates. The second class of materials are essentially alumina free silicates. These crystalline materials can include crystalline silica polymorphs, e.g., silicalite, chromia silicates, e.g., CZM, and ferrosilicates, e.g., U.S. Pat. No. 4,238,318.

All of these materials have the ability of sorting molecules based on the size or the shape, or both of the molecules. The larger pore size materials will admit larger molecules than the smaller pore size materials. Intermediate pore size silicaceous crystalline molecular sieves have the unique characteristics of being able to differentiate between large molecules and molecules containing quaternary carbon atoms on the one hand, and smaller molecules on the other. Thus, the intermediate pore size materials have surprising catalytic selectivities by reason of their effective pore apertures, as well as highly desirable and surprising catalytic activity and stability when compared to larger pore size crystalline molecular sieves.

By "intermediate pore size," as used herein, is meant an effective pore aperture in the range of about 5 to 6.5 Angstroms when the molecular sieve is in the H-form. Molecular sieves having pore apertures in this range tend to have unique molecular sieving characteristics. Unlike small pore zeolites such as erionite and chabazite, they will allow hydrocarbons having some branching into the molecular sieve void spaces. Unlike larger pore zeolites such as the faujasites and mordenites, they can differentiate between n-alkanes and slightly branched alkanes on the one hand and larger branched alkanes having, for example, quaternary carbon atoms.

The effective pore size of the molecular sieves can be measured using standard adsorption techniques and hydrocarbonaceous compounds of known minimum kinetic diameters. See Breck, Zeolite Molecular Sieves, 1974 (especially Chapter 8) and Anderson et al, J. Catalysis 58, 114 (1979), both of which are incorporated by reference.

Intermediate pore size molecular sieves in the H-form will typically admit molecules having kinetic diameters of 5.0 to 6.5 Angstroms with little hindrance. Examples of such compounds (and their kinetic diameters in Angstroms) are: n-hexane (4.3), 3-methylpentane (5.5), benzene (5.85), and toluene (5.8). Compounds having kinetic diameters of about 6 to 6.5 Angstroms can be admitted into the pores, depending on the particular sieve, but do not penetrate as quickly and in some cases are effectively excluded. Compounds having kinetic diameters in the range of 6 to 6.5 Angstroms include: cyclohexane (6.0), 2,3-dimethylbutane (b 6.1), m-xylene (6.1), and 1,2,3,4-tetramethylbenzene (6.4). Generally, compounds having kinetic diameters of greater than about 6.5 Angstroms do not penetrate the pore apertures and thus are not absorbed into the interior of the molecular sieve lattice. Examples of such larger compounds include: o-xylene (6.8), hexamethybenzene (7.1), 1,3,5-trimethylbenzene (7.5), and tributylamine (8.1).

A preferred effective pore size range is from about 5.3 to about 6.2 Angstroms. Among the materials falling within this range are the zeolite ZSM-5, the crystalline silica polymorphs, silicalite and RE 29,948 organosilicates, and the chromia silicate, CZM.

In performing adsorption measurements to determine pore size, standard techniques are used. It is convenient to consider a particular molecule as excluded if it does not reach at least 95% of its equilibrium adsorption value on the zeolite in less than about 10 minutes (p/po=0.5; 25° C.).

Examples of intermediate pore size silicaceous crystalline molecular sieves include zeolites such as CZH-5 and members of the ZSM series, e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-21, ZSM-23, ZSM-35, and ZSM-38. ZSM-5 is described in U.S. Pat. Nos. 3,700,585, 3,702,886 and 3,770,614; ZSM-11 is described in U.S. Pat. No. 3,709,979; ZSM-12 is described in U.S. Pat. No. 3,832,449; ZSM-21 and ZSM-38 are described in U.S. Pat. No. 3,948,758; ZSM-23 is described in U.S. Pat. No. b 4,076,842; ZSM-35 is described in U.S. Pat No. 4,016,245; CZH-5 is disclosed in Ser. No. 166,863, Hickson, filed July 7, 1980 now abandoned. These patents and specifications are incorporated herein by reference. The intermediate pore size materials can include "crystalline admixtures" which are thought to be the result of faults occurring within the crystal or crystallite area during the synthesis of the zeolites. The "crystalline admixtures" are themselves zeolites but have characteristics in common, in a uniform or nonuniform manner, to what the literature reports as distinct zeolites. Examples of crystalline admixtures of ZSM-5 and ZSM-11 are disclosed and claimed in U.S. Pat. No. 4,229,424, Kokotailo, Oct. 21, 1980 (incorporated by reference). Th crystalline admixtures are themselves intermediate pore size zeolites and are not to be confused with physical admixtures of zeolites in which distinct crystals or crystallites of different zeolites are physically present in the same catalyst composite or hydrothermal reaction mixture.

Other examples of intermediate pore size silicaceous crystalline molecular sieves include crystalline silica polymorphs which, as described before, are essentially alumina free.

"Essentially alumina free," used herein, is meant the product silica polymorph (or essentially alumina-free silicaceous crystalline molecular sieve) has a silica:alumina mole ratio of greater than 200:1, preferably greater than 500:1, and more preferably greater than 1000:1. The term "essentially alumina free" is used because it is difficult to prepare completely aluminum free reaction mixtures for synthesizing these materials. Especially when commercial silica sources are used, aluminum is almost always present to a greater or lesser degree. The hydrothermal reaction mixtures from which the essentially alumina free crystalline silicaceous molecular sieves are prepared can also be referred to as being substantially aluminum free. By this usage is meant that no aluminum is intentionally added to the reaction mixture, e.g., as an alumina or aluminate reagent, and that to the extent aluminum is present, it occurs only as a contaminant in the reagents.

Intermediate pore size crystalline silicas include silicalite, disclosed in U.S. Pat. No. 4,061,724; the "RE 29,948 organosilicates" as disclosed in RE 29,948; and CZH-9, Ser. No. 264,767, Hickson, filed May 18, 1981. Intermediate pore size silicas, ferrosilicates and galliosilicates are disclosed in U.S. Pat. No. 4,238,318, Kouwenhoven et al, Dec. 9, 1980. Intermediate pore size chromia silicates, CZM, are disclosed in Ser. No. 160,618, Miller, filed June 28, 1980. All of these are incorporated by reference.

The most preferred molecular sieves are the ZSM-5 type zeolites.

The H-form and the Zn-form and mixture thereof, as well as rare earth-exchange modifications thereof, as may be required herein, are obtained by conventional base- and/or ion-exchange methods routinely employed in the zeolite art, including customary zeolite drying and calcining steps. Preferably, the molecular sieves herein have minimal sodium contents, for example by weight less than about 100 ppm, although the molecular sieves having a larger sodium content exhibit relatively useful catalytic activities for present purposes.

Process Conditions

The process conditions satisfactory for use herein include:

    ______________________________________                                                        Broad Range                                                                             Preferred Range                                        ______________________________________                                         Temperature, °C.                                                                         260-540    290-425                                            Pressure, Atm. g.                                                                                7-200      14-100                                            Hydrogenation Rate, SCM/m.sup.3                                                                  85-340     85-170                                            LHSV, V/V/Hr      0.1-100   0.2-10                                             Per-Pass Conversion, %                                                                           5-75       8-25                                              ______________________________________                                    

Hydrocarbon Feedstocks

The feedstocks suitable for use herein can be selected, for example, from the group consisting of petroleum distillates, e.g., distillates having a normal boiling point of from about 315° C. to 590° C., solvent-deasphalted petroleum residua, and shale oils. The feedstocks can contain substantial amounts of materials boiling above 95° C., preferably substantial amounts of materials boiling in the normal boiling point range 180° to 510° C., and more preferably in the range 205° to 595° C. Suitable feedstocks include those heavy distillates normally defined as heavy straight-run gas oils and heavy cracked cycle oils, as well as conventional FCC feed and portions thereof. Cracked stocks may be obtained from thermal or catalytic cracking of various stocks, including those obtained from petroleum, gilsonite, and shale. As discussed hereinafter, the feedstocks may have been subjected to a hydrofining and/or hydrogenation treatment, which may have been accompanied by some hydrocracking, before being supplied to the present process. The feedstock can have an initial boiling point of a least about 315° C.

Nitrogen Content of Feedstocks

While the process herein can be practiced with utility when the feed contains organic nitrogen (nitrogen-containing impurities), for example as much as several thousand parts per million by weight of organic nitrogen, it is preferred that the organic nitrogen content of the feed be less than 50, more preferably less than 10, ppmw. Especially good results, in terms of activity and length of catalyst cycle (period between successive regenerations or start-up and first regeneration), are experienced when the feed contains less than 10 ppmw of organic nitrogen. This is surprising in view of the art (see, for example, U.S. Pat. No. 3,894,938).

Sulfur Content of Feedstocks

The presence of organic sulfur (sulfur-containing impurities) in the feedstock does not appear to deleteriously affect the desired hydrocracking of the feed, for example in terms of activity and catalyst life. In fact, hydrodesulfurizing of the feed of organic sulfur is in large part a significant concurrent reaction. However, the resulting product, in general, will contain at least some thiols and/or thioethers as a result of inter-reaction of hydrogen sulfide and olefinic hydrocarbons in the effluent product stream. Thus, it may be desirable in some instances that the feed prior to use in the process herein be hydrofined or hydrotreated for at least a substantial removal of both organic sulfur- and nitrogen-containing compounds.

Upstream hydrodenitrogenation can be performed in a separate reactor or in the reactor with the molecular sieve containing catalyst. When a separate hydrodenitrogenation reactor is used, it may be desirable to remove, e.g. flash, light gaseous products such as NH₃ upstream of the ZSM-5 containing reactor. If the hydrotreating is performed in the same reactor, the molecular sieve-containing catalyst is disposed in one or more layers downstream of an active hydrodenitrogenation catalyst. The single reactor should preferably be operated under hydrotreating conditions sufficient to reduce the organic nitrogen of the feed to 10 ppmw or less before the feed encounters the molecular sieve-containing layer. The volume of hydrodenitrogenation catalyst relative to molecular sieve-containing catalyst can vary over a wide range, such as from about 1 to 1 to 100 to 1, preferably at least 2 to 1 and more preferably at least 5 to 1. The ratio depends upon such parameters as

(a) the organic nitrogen content of the feedstock;

(b) the hydrodenitrification and hydrocracking activities of the upstream hydrotreating catalyst;

(c) the degree of overall hydrocracking desired.

An additional advantage of employing an upstream active hydrodenitrogenation catalyst is that much of the hydrocracking can be carried out over the hydrodenitrogenation catalyst, which would normally have a hydrocracking activity lower than the catalyst containing the molecular sieve. In this manner the presence of the ZSM-5-containing catalyst increases the overall hydrocracking activity of the combined catalyst charge, while the light gas make that accompanies hydrocracking over the molecular sieve can be partially avoided.

The upstream hydrotreating catalysts can be any of the conventional catalysts having hydrodenitrogenation and hydrocracking activity. See, for example, U.S Pat. No. 3,401,125 incorporated herein by reference. In general such hydrotreating catalysts are porous composites of inorganic matrix oxides such as alumina, silica, magnesia, etc. which contain one or more hydrogenation components such as transition elements, particularly elements of Group VIB or Group VIII of the Periodic Table of the Elements. Handbook of Chemistry and Physics, 45th Ed., Chemical Rubber Company. The Group VIB and/or Group VIII or other transition elements can be present as metals, oxides, or sulfides. The hydrotreating catalyst can also contain promoters such as phosphorus, titanium and other materials known in the art, present as metals, oxides or sulfides. The upstream hydrotreating catalyst need not contain a zeolite component. Typical upstream hydrogenation catalysts suitable for use herein contain 10 to 30 weight % amorphous silica, 20 to 40 weight % amorphous alumina, 15 to 30 weight % Group VIB metal oxide, preferably WO₃, 5 to 15 weight % Group VIII metal oxide, preferably NiO, and 2 to 15 weight % of a promoter oxide, preferably TiO₂. The hydrotreating catalyst should have an average pore size in the range of about 30 to 200 Angstroms and a surface area of at least about 150 square meters per gram.

EXAMPLES

The following examples illustrate the best mode presently contemplated for carrying out the invention.

Example 1

A catalyst suitable for use herein was prepared using quantities of the various starting materials sufficient to produce a composite of the following composition:

    ______________________________________                                                       Wt. % of Total                                                   Component     Composite                                                        ______________________________________                                         NiO           8.5                                                              WO.sub.3      21.0                                                             TiO.sub.2     6.7                                                              Al.sub.2 O.sub.3                                                                             25                                                               SiO.sub.2     22                                                               HZSM-5        16.8                                                             Total         100.0                                                            ______________________________________                                    

The following steps are employed in the preparation of the above catalyst:

(1) An aqueous acid solution is prepared by adding AlCl₃, TiCl₄ and NiCl₂ to an aqueous solution of acetic acid;

(2) Three aqueous alkaline solutions are prepared: (a) a sodium silicate solution; (b) a sodium tungstate solution; and (c) an ammonium solution containing sufficient ammonia such that, upon combining these alkaline solutions with the acidic solution, coprecipitation of all of the metal-containing components occurs at a neutral pH of about 7;

(3) The acid and alkaline solutions of (1) and (2) are combined and coprecipitation of all of the metal-containing components of these solutions occurs at a pH of about 7, resulting in a slurry of precipitated metal oxides and/or hydroxides in a silica-alumina cogel;

(4) H-ZSM-5-type crystalline aluminosilica zeolite in finely divided form is added to the slurry with thorough mixing;

(5) The slurry from (4) is filtered to produce a hydrogel cake which is then washed repeatedly with portions of dilute aqueous ammonium acetate solution to remove ionic sodium and chloride impurities from both the hydrogel and the zeolite;

(6) The washed cake is then shaped, for example by extrusion through a die about 0.3 cm in diameter and cut in similarly sized lengths, dried and calcined at about 510° C. in a flowing air stream in an oven for about 5 hours.

The finished catalyst is characterized by (1) a porous silica-alumina-titania polygel matrix in which the silica component is highly dispersed, (2) a hydrogenation component which is dispersed in the matrix, and (3) a zeolite component which is substantially free of catalytic hydrogenation metals and which is also dispersed in the matrix, there being little or none of the hydrogenation metals therein in intimate combination with the ZSM-5 zeolite. Other physical characteristics of the catalyst include a surface area of about 360 m² /g, and a pore volume of about 0.36 cc/g. The catalyst is designated catalyst A.

Examples 2 and 3

Under the conditions and using separate portions of the catalyst described in the embodiment above, the low nitrogen feed described therein (Example 2) and a feed having the following characteristics (Example 3):

    ______________________________________                                         Gravity, °API 22.9                                                      Sulfur, ppmw         2100                                                      Nitrogen, ppmw       870                                                       Pour Point, °C.                                                                              29                                                        Hydrocarbon Distribution, LV %                                                 Paraffins            19                                                        Naphthenes           25                                                        Aromatics            17                                                        Sulfur Compounds     22                                                        Distillation, %, °C.                                                    5/30                 374/413                                                   50/70                445/467                                                   90/EP                504/537                                                   ______________________________________                                    

were hydrocracked. The results for these comparative examples are shown in the FIGURE. The data therein demonstrate the drastic effect of nitrogen-containing impurities in reducing catalyst activity of ZSM-5-containing hydrocracking catalysts. In Example 2, after about 500 hours on stream, sufficient alkylamine was added to the feed to provide a nitrogen content of about 800 ppmw. As shown in the FIGURE, there resulted an immediate reduction in the activity of the catalyst. These examples demonstrate that the molecular sieve-containing hydrocracking catalysts will be extremely sensitive to nitrogen-containing impurities. That nitrogen-containing impurity in the feed markedly reduces the pour point reduction is evident from the following:

    ______________________________________                                                         Pour Point, °C.                                         ______________________________________                                         Feed for Example 2                                                                               29                                                           Product from Example 2                                                                            2                                                           Feed for Example 3                                                                               29                                                           Product from Example 3                                                                           21                                                           ______________________________________                                    

Example 4

In this example the catalyst was, for practical purposes, identical to that of Examples 2 and 3 except that the molecular sieve component thereof was an ultrastable HY sieve (faujasite). The conditions and feed employed were the same as in Example 2. From a comparison of the data for Examples 2 and 3 as shown in the FIGURE, the performance of the catalyst of the present invention, in terms of the time-temperature relationship, was markedly superior. The pour points of the products were as follows:

    ______________________________________                                                Example 2                                                                               2° C.                                                          Example 4                                                                              29° C.                                                   ______________________________________                                    

In terms of pour point of the product, the advantage of the catalyst of the present invention over HY-sieve-containing catalyst is also remarkable.

Examples 5 and 6

In a further comparison the catalysts used in Examples 2 and 4 were used in a high per pass conversion of a denitrified Empire vacuum gas oil feed having by volume the following percentage composition:

    ______________________________________                                                 Paraffins                                                                              24                                                                     Naphthenes                                                                             49                                                                     Aromatics                                                                              27                                                             ______________________________________                                    

The conditions employed were as follows:

    ______________________________________                                                         Example 5                                                                              Example 6                                                              (HY-Sieve)                                                                             (ZSM)                                                  ______________________________________                                         Per Pass Conversion                                                                               80        80                                                LHSV, V/V/Hr.        1.4       1.4                                             Average Cat. Temp., °C.                                                                    334       311                                               Total Pressure, Psig                                                                             1328      1324                                               H.sub.2, Mean Pressure, Psia                                                                     1168      1113                                               Total Gas In, SCF/B                                                                              6533      6834                                               Recycle Gas, SCF/B                                                                               5573      5541                                               ______________________________________                                    

and the normalized (no loss) weight percent product yields were as follows:

    ______________________________________                                                      Example 5                                                                              Example 6                                                 ______________________________________                                         C.sub.1        0.01      0.01                                                  C.sub.2        0.2       0.3                                                   C.sub.3        3.4       13.5                                                  i-C.sub.4      9.7       16.6                                                  n-C.sub.4      3.9       9.3                                                   C.sub.5 -180° F.                                                                       23.2      34.6                                                  180°-380° F.                                                                    61.7      28.3                                                  Total C.sub.5 +                                                                               84.9      63.0                                                  ______________________________________                                    

While the C₅ + yield obtained in Example 5 was superior to that obtained in Example 6, the former, as shown by chromatographic analysis, had a large content of normal and slightly branched paraffins whereas the product obtained in the latter contained little or none of these paraffins. Thus, the ZSM-containing catalyst effectively removed low-octane-contributing paraffins from the product.

Examples 7 and 8

Two hydrocracking runs were carried out with raw petroleum vacuum gas oil feed. In Example 7, the feed was passed downwardly through a fixed bed reactor containing a charge of an active hydrodenitrogenation catalyst designated as catalyst B. In Example 8, the feedstock was passed downwardly under identical conditions through a fixed bed reactor containing 10 parts by weight catalyst B over one part of a catalyst substantially identical to catalyst A. Catalyst B was a cogelled amorphous SiO₂ /Al₂ O₃ catalyst containing about 8.6% NiO, 21.5% WO₃ and 4.6% TiO₂, having a SiO₂ /Al₂ O₃ ratio of about 1, with an average pore volume of about 0.4 cc/gram and an average pore diameter of about 50 Angstroms. Such catalysts can be prepared for example by the method of U.S. Pat. No. 3,401,125.

The hydroprocessing conditions of Examples 7 and 8 included a space velocity (LHSV) of 1.2, a total pressure of 115 atmospheres, and a hydrogen feed rate of 3560 cubic meters per cubic meter of hydrocarbon feed. The temperature was varied to provide a constant product quality of 70 weight percent material boiling below 338° C. The hydrogenation conditions were selected to provide a feed of 1 ppmw nitrogen content to the ZSM-5-containing catalyst region of the reactor of Example 8. The results of these tests are depicted in the following table:

    ______________________________________                                                            Example 7                                                                              Example 8                                           ______________________________________                                         Temperature after 280 hours, °C.                                                             423       410                                             Pour point of 200-340° C. product, °C.                                                -32       -37                                             Pour point of 340° C.+ product, °C.                                                   20        20                                              Yield, wt. %                                                                   C.sub.1 -C.sub.4     4.4.      5.4                                             C.sub.5 -80° C.                                                                              9.4       10.7                                            80-200° C.    19.7      23.1                                            200-340° C.   37.7      31.6                                            340° C.+      28.8      29.2                                            ______________________________________                                     

What is claimed is:
 1. A hydrocracking process comprising contacting a hydrocarbon feed containing substantial amounts of materials boiling above 95° C. in a reaction zone with hydrogen and a catalyst under hydrocracking conditions, wherein said catalyst comprises a composite containing:(A) a porous amorphous matrix selected from the group consisting of alumina-silica, alumina-silica-titania and alumina-silica-zirconia polygels, said polygel having an alumina-to-silica weight ratio in the range of from about 0.2-20 to 1, respectively; (B) a hydrogenation component of (1) nickel or cobalt or any combination thereof in an amount, calculated as metal, in the range of from about 1 to 10 weight percent of said matrix, and (2) molybdenum or tungsten, or any combination thereof, in an amount, calculated as metal in the range of from about 5 to 25 weight percent of said matrix, said hydrogenation component being (1) in the form of metal or oxide or sulfide or any combination thereof and (2) dispersed through said matrix; and (C) a finely divided intermediate pore size silicaceous crystalline molecular sieve component substantially in the ammonium or hydrogen form, said molecular sieve being (1) substantially free of such hydrogenation component, (2) dispersed through said matrix and (3) selected from the group consisting of (i) crystalline aluminosilicates of the ZSM series including crystalline admixtures of members of the ZSM series and (ii) essentially alumina-free silicates of the crystalline silica polymorph or chromia silicate or ferrosilicate families.
 2. The process as in claim 1 wherein said matrix of said catalyst contains (1) at least 15 weight percent of silica, and (2) an amount of titania, calculated as metal, in the range of from about 1 to 10 weight percent and said composite contains an amount of said molecular sieve in the range of from about 1 to 50 weight percent and has a surface area above about 200 m² /gram.
 3. The process as in claim 2 wherein said amount of molecular sieve is about 17%, said hydrogenating component is nickel and tungsten in amounts of about 7 and 17 weight percent, respectively, and wherein said matrix contains about 7 weight percent of titania.
 4. A process as in claim 1 wherein said feed has a content of nitrogen-containing impurities, calculated as nitrogen, which is below about 10 ppmw.
 5. A process as in claim 4 wherein said feed is a petroleum distillate and at least a fraction of the resulting product is a lube oil having, relative to said feed, an improved pour point.
 6. A process as in claim 1 wherein said hydrocracking conditions are controlled so as to maintain a feed conversion level in the range of from about 5 to 75 volume percent.
 7. A process as in claim 1 wherein said feed has an initial normal boiling point of at least about 315° C.
 8. A process as in claim 5 wherein said distillate has a normal boiling point in the range of from about 315° C. to 590° C.
 9. A process as in claim 1 wherein said hydrocarbon feed is selected from the group consisting of petroleum distillates, solvent deasphalted residua, and shale oils.
 10. A process as in claim 4 wherein said catalyst is disposed downstream of a reaction zone in which a hydrocarbon feed is contacted under hydroprocessing conditions with an active hydrodenitrogenation catalyst.
 11. A process as in claim 10 wherein said hydrodenitrogenation catalyst is disposed in a single reactor with said composite containing a molecular sieve component.
 12. A process as in claim 11 wherein said reactor contains at least 2 parts by volume hydrodenitrogenation catalyst upstream of one part by volume of said composite containing a molecular sieve component.
 13. A process as in claim 10, 11 or 12 in which said hydrodenitrification catalyst is a porous composite containing an inorganic matrix oxide selected from the group consisting of alumina, silica, magnesia, and mixtures thereof, and at least one hydrogenation component selected from Group VIB and Group VIII elements, present as metals, oxides or sulfides.
 14. A hydrocracking process comprising contacting a hydrocarbon feed containing substantial amounts of materials boiling above 95° C., said feed having a content of nitrogen-containing impurities, calculated as nitrogen, which is below about 10 ppmw, in a reaction zone with hydrogen and a catalyst under hydrocracking conditions wherein said catalyst comprises a composite containing:(A) A porous amorphous matrix selected from the group consisting of alumina-silica, alumina-silica-titania and alumina-silica-zirconia polygels, said polygels having an alumina-silica weight ratio in the range of from about 0.2-20 to 1 respectively; (B) A hydrogenation component of (1) nickel in an amount, calculated as metal, in the range of from about 1 to 10 weight percent of said matrix, and (2) tungsten, in an amount calculated as metal, in the range of from about 5 to 25 weight percent of said matrix, said hydrogenation component being in the form of metal or oxide or sulfide or any combination thereof and (3) dispersed through said matrix; and (C) A finely divided intermediate pore size silicaceous crystalline molecular sieve component substantially in the ammonium or hydrogen form, said molecular sieve being (1) substantially free of such hydrogenation component, (2) dispersed through said matrix and (3) selected from the group consisting of (i) crystalline aluminosilicates of the ZSM series including crystalline admixtures of members of the ZSM series and (ii) essentially alumina-free silicates of the crystalline silica polymorphs or chromia silicate or ferrosilicate families.
 15. The process as in claim 14 wherein said matrix of said catalyst contains (1) at least 15 weight percent of silica, and (2) an amount of titania, calculated as metal, in the range of from about 1 to 10 weight percent and said composite contains an amount of said molecular sieve in the range of from about 1 to 50 weight percent and has a surface area above about 200 m² /gram.
 16. The process as in claim 15 wherein said amount of molecular sieve is about 17%, said hydrogenating component is nickel and tungsten in amounts of about 7 and 17 weight percent, respectively, and wherein said matrix contains about 7 weight percent of titania.
 17. A process as in claim 14 wherein said feed is a petroleum distillate and at least a fraction of the resulting product is a lube oil having, relative to said feed, an improved pour point.
 18. A process as in claim 14 wherein said hydrocracking conditions are controlled so as to maintain a feed conversion level in the range of from about 5 to 75 volume percent.
 19. A process as in claim 14 wherein said feed has an initial normal boiling point of at least about 315° C.
 20. A process as in claim 17 wherein said distillate has a normal boiling point in the range of from about 315° C. to 590° C.
 21. A process as in claim 14 wherein said catalyst is disposed downstream of a reaction zone in which a hydrocarbon feed is contacted under hydroprocessing conditions with an active hydrodenitrogenation catalyst.
 22. A process as in claim 21, in which said hydrodenitrification catalyst is a porous composite containing an inorganic matrix oxide selected from the group consisting of alumina, silica, magnesia, and mixtures thereof, and at least one hydrogenation component selected from Group VIB and Group VIII elements, present as metals, oxides or sulfides.
 23. A process as in claim 1, 4, 14 or 22 wherein said intermediate pore silicaceous crystalline molecular sieve is an essentially alumina-free silicate.
 24. A process as in claim 23 wherein said molecular sieve has a silica-alumina atomic ratio of greater than 500-1.
 25. A process as in claim 23 wherein said molecular sieve is silicalite.
 26. A process as in claim 23 wherein said molecular sieve is substantially in the hydrogen form.
 27. A process according to claim 1 wherein the molecular sieve component is a member of the ZSM series.
 28. A process according to claim 1 wherein the molecular sieve component is silicalite.
 29. A process according to claim 1 wherein the molecular sieve component is a chromia silicate.
 30. A process according to claim 1 wherein the chromia silicate component is a CZM zeolite.
 31. A process according to claim 1 wherein the molecular sieve component has an effective pore size range from about 5 to about 6.5 Angstroms. 